CN112352036B - Hydrocarbon mixtures exhibiting a unique branched structure - Google Patents

Abstract

Provided herein are hydrocarbon mixtures with controlled structural properties that address performance requirements for the final lubricant driven by stricter environmental and fuel economy regulations. The branching characteristics of the hydrocarbon molecules are controlled to provide compositions having unique and superior viscosity-temperature dependence and Noack volatility. An important aspect of the invention relates to a saturated hydrocarbon mixture of which at least 80% of the molecules have an even number of carbon numbers and a branching character BP/BI ≧ 0.6037 (internal alkyl branch) +2.0, in which on average at least 0.3 to 1.5 internal methyl branches are located more than 4 carbons from the terminal carbon when analyzed by carbon NMR. Saturated hydrocarbon mixtures having such unique branching structures consistently exhibit outstanding performance in cold cranking simulated viscosity (CCS) versus Noack volatility correlations, which allows the formulation of low viscosity engine oils with improved fuel economy.

Description

Hydrocarbon mixtures exhibiting a unique branched structure

Technical Field

High performance hydrocarbon mixtures have been developed which have a unique combination of properties and which exhibit excellent low temperature performance and volatility.

Background

Base stocks are commonly used in the production of a variety of lubricants, including automotive lubricating oils, industrial oils, turbine oils, lubricating esters, metal working fluids, and the like. They are also used as process oils, white oils and heat transfer fluids. Finished lubricants generally consist of two components: base oil and additives. The base stock, which may be one base stock or a mixture of base stocks, is the major component in these finished lubricants and makes a significant contribution to the properties of the finished lubricant such as viscosity and viscosity index, volatility, stability and low temperature properties. Typically, a small number of base stocks are used to make a wide variety of finished lubricants by varying the mixture of individual base stocks and individual additives.

The American Petroleum Institute (API) classifies base stocks into five categories based on their saturates content, sulfur level, and viscosity index (table 1 below). I. Group II and III base stocks are mostly obtained from crude oil via extensive processing such as solvent refining for group I and hydrotreating for group II and group III. Certain group III basestocks may also be produced from synthetic hydrocarbon liquids via gas-to-liquid processes (GTL) and obtained from natural gas, coal or other fossil resources. Group IV basestocks (polyalphaolefins (PAOs)) are produced by the oligomerization of alpha olefins, such as 1-decene. Group V basestocks include all basestocks not belonging to groups I-IV, such as naphthenic basestocks, polyalkylene glycols (PAGs), and esters. Most feedstocks used for large-scale base stock manufacture are non-renewable.

TABLE 1 API base oil classification (API 1509 appendix E)

Automotive engine oils are by far the largest market for basestocks. The automotive industry has established more stringent performance specifications for engine oils due to requirements for lower emissions, longer drain intervals, and better fuel economy. In particular, automotive OEMs (original equipment manufacturers) have driven the use of lower viscosity engine oils, such as 0W-20 to 0W-8, to reduce friction losses and achieve fuel economy improvements. Base stocks having lower Noack volatility in engine oils allow the formulation to retain the designed viscosity for longer run times (which allows for increased fuel economy retention) and longer drain intervals, as discussed in US 6300291. The use of group I and group II in 0W-xx engine oils is highly limited because the formulations blended with them fail to meet the performance specifications of 0W-xx engine oils, which results in increased demand for group III and group IV base stocks.

Group III base stocks are produced primarily from Vacuum Gas Oil (VGO) by hydrocracking and catalytic dewaxing (e.g., hydroisomerization). Group III base stocks may also be produced by catalytic dewaxing of slack wax from solvent refining or by catalytic dewaxing of fischer-tropsch synthesized waxes derived from natural gas or coal based raw materials (also known as gas to liquid base oils (GTL)).

The manufacture of group III basestocks from VGO is discussed in U.S. patent nos. 5993644 and 6974535. Their boiling point distribution is typically higher when compared to PAOs of the same viscosity, which results in their higher volatility than PAOs. In addition, group III basestocks typically have a higher cold start viscosity (i.e. dynamic viscosity according to ASTM D5293, CCS) than group IV basestocks at the same viscosity.

GTL base stock processing is described in U.S. patent nos. 6420618 and 7282134, and U.S. patent application publication No. 2008/0156697. For example, the latter publication describes a process for producing base stocks from fischer-tropsch synthesis products, fractions of which having a suitable boiling point range are subjected to hydroisomerisation to produce GTL base stocks.

GTL base stocks of such structure and properties are described, for example, in U.S. patent nos. 6090989 and 7083713, and U.S. patent application publication No. 2005/0077208. In U.S. patent application publication 2005/0077208 lubricant base stocks are described having optimized branching with alkyl branches concentrated toward the molecular center to improve the cold flow properties of the base stock. However, the pour point of GTL base stocks is typically poorer than PAO or other synthetic hydrocarbon base stocks.

Another concern with GTL base stocks is severely limited commercial supply due to the prohibitive large capital requirements of new GTL manufacturing facilities. There is also a need to obtain low cost natural gas to profitably produce GTL base stocks. Furthermore, since GTL base stocks are typically distilled from isomerate with a broad boiling point profile, this process results in relatively low yields for base stocks of the desired viscosity when compared to typical PAO processes. Due to these monetary and yield limitations, there is currently only a single manufacturing facility for group III + GTL base stocks, which exposes GTL-using formulations to the risk of supply chain and price fluctuations.

Polyalphaolefins (PAO) or group IV basestocks are prepared by reacting a Polyalphaolefin (PAO) or group IV basestock in a Friedel-crafts catalyst such as AlCl₃、BF₃Or BF₃Alpha-olefins are polymerized in the presence of the complex. For example, 1-octene, 1-decene, and 1-dodecene have been used to make PAOs with a wide range of viscosities ranging from low viscosity at 100 ℃ of low molecular weight and about 2cSt to high molecular weight viscous materials with a viscosity at 100 ℃ in excess of 100 cSt. The polymerization reaction is typically carried out in the absence of hydrogen; the lubricant range product is thereafter refined or hydrogenated to reduce residual unsaturation. Processes for producing PAO-based lubricants are disclosed in, for example, U.S. patent nos. 3382291;4172855;3742082;3780128;3149178;4956122;5082986; 745629; 7544850; and U.S. patent application publication 2014/0323665. Prior art efforts to prepare various PAOs that can meet the increasingly stringent performance requirements of modern lubricants and automotive engine oils have particularly favored low viscosity polyalphaolefin base stocks derived from 1-decene alone or in certain blends with other mineral oils. However, polyalphaolefins derived from 1-decene can be prohibitively expensive due to its limited supply. Attempts to overcome the availability limitations of 1-deceneHave resulted in the production of PAOs from C8-C12 mixed alpha olefin feeds, which reduces the amount of 1-decene required to impart the properties. However, they still do not completely eliminate the need to provide 1-decene as the primary olefin feedstock due to performance concerns.

Similarly, previous efforts to use linear alpha olefins in the C14-C20 range have produced polyalphaolefins with unacceptably high pour points that are not suitable for use in a variety of lubricants, including 0W engine oils.

Therefore, there remains a need for a base stock composition that has properties within a commercially acceptable range, for example for use in automotive and other applications, and such properties include one or more of the following: viscosity, noack volatility, and low temperature cold start viscosity. Furthermore, there remains a need for base stock compositions having improved properties and methods of making the same, wherein the base stock compositions have a reduced amount of 1-decene incorporated therein, and may even preferably eliminate the use of 1-decene in their manufacture.

In addition to the technical needs of the automotive industry, environmental awareness and regulations are driving manufacturers to use renewable feedstocks and raw materials in the production of base stocks and lubricants. It is known that esters of renewable and biological origin and some group III hydrocarbon basestocks (US 9862906B 2) have been used in applications such as refrigeration compressor lubricants, hydraulic oils and metal working fluids, and more recently in automotive and industrial lubricants (US 20170240832 A1). Common biological sources of hydrocarbons are natural oils, which may be derived from plant sources such as canola (canola) oil, castor oil, sunflower oil, rapeseed oil, peanut oil, soybean oil and tall oil, or palm oil. Other commercial sources of hydrocarbons include engineered microorganisms such as algae or yeast.

Due to the increasing demand for high performance lubricant base stocks, there is a constant need for improved hydrocarbon mixtures. Industry demands that these hydrocarbon mixtures have excellent Noack volatility and low temperature viscosity properties that can meet the more stringent engine oil requirements, preferably from renewable sources.

Summary of The Invention

The present invention relates to a saturated hydrocarbon mixture with well controlled structural properties that addresses the performance requirements for automotive engine oils driven by more stringent environmental and fuel economy regulations. The branching properties of the hydrocarbon molecules are controlled to consistently provide compositions having a surprising correlation of CCS viscosity (ASTM D5329) and Noack volatility (ASTM D5800) at-35 ℃.

An important aspect of the invention relates to a saturated hydrocarbon mixture having more than 80% of the molecules with an even number of carbon numbers (according to FIMS) and the mixture exhibiting a branching character BP/BI of ≥ 0.6037 (internal alkyl branches per molecule) +2.0, and, when the hydrocarbon mixture is analyzed by carbon NMR ensemble, having an average of at least 0.3-1.5 methyl branches per molecule.

One way to synthesize the hydrocarbon mixtures disclosed herein is by oligomerizing C14-C20 alpha or internal olefins, followed by hydroisomerization of the oligomers. The use of C14-C20 olefins will alleviate the need for high price 1-decene and other crude oil or syngas based olefins as feedstocks, and alternative sources of olefin feedstocks such as those derived from C14-C20 alcohols can be utilized. The hydrocarbon composition is derived from one or more olefin comonomers, wherein the olefin comonomer is oligomerized to dimers, trimers, and higher oligomers. The oligomer is then subjected to hydroisomerization. The resulting hydrocarbon mixture has excellent pour point, volatility and viscosity characteristics as well as additive solubility.

Another aspect of the invention is the use of the disclosed saturated hydrocarbon mixture as a base stock for a finished lubricant formulation, wherein the finished lubricant formulation comprises the saturated hydrocarbon mixture as a base stock, and one or more lubricant or lubricating ester additives.

Drawings

FIG. 1 shows the correlation between BP/BI and internal alkyl branching per molecule for various hydrocarbons including low viscosity PAO made from 1-decene and 1-dodecene, GTL base oils, and hydroisomerized hexadecene oligomers. The straight line in the figure depicts the equation BP/BI = -0.6037 (internal alkyl branches per molecule) +2.0.

FIG. 2 shows the correlation between BP/BI and 5+ methyl branches per molecule for various hydrocarbons including low viscosity PAO made from 1-decene and 1-dodecene, GTL base oils, and hydroisomerized hexadecene oligomers. It demonstrates that the 5+ methyl branch per molecule of the hydrocarbon mixture disclosed in this patent falls within a unique range of 0.3 to 1.5.

FIG. 3 shows the correlation between NOACK volatility and CCS at-35 ℃ for various hydrocarbons including low viscosity PAO made from 1-decene and 1-dodecene, GTL base oils, group III base oils, and hydroisomerized hexadecene oligomers. The solid and dashed lines depict the upper and lower limits of Noack compared to CCS at-35 ℃, respectively, exhibited by the unique hydrocarbon mixtures of the present invention, which are Noack =2750 (CCS at-35 ℃)^(-0.8)+2 and NOACK =2750 (CCS at-35 ℃), and^(-0.8)-2。

FIG. 4 is an enlarged view of the CCS range of 800-2800cP at-35 deg.C of FIG. 3.

Detailed description of the invention

Disclosed herein is a saturated hydrocarbon mixture having a unique branched structure characterized by NMR, which makes it suitable for use as a high quality synthetic base stock. The hydrocarbon mixtures have outstanding properties, including very low volatility, good low temperature properties, etc., which are important performance attributes of high quality base stocks. Specifically, according to FIMS, the mixture comprises more than 80% of the molecules having an even number of carbon numbers. The branching characteristics of the hydrocarbon mixture by NMR include BP/BI ≥ 0.6037 (internal alkyl branching per molecule) +2.0. Further, on average, at least 0.3 to 1.5 internal methyl branches are located more than four carbons from the terminal carbon. Saturated hydrocarbons having this unique branching structure exhibit a surprising cold cranking simulated viscosity (CCS) versus Noack volatility correlation that is beneficial for blending low viscosity automotive engine oils.

In one embodiment, the hydrocarbon mixture described herein is the product of olefin oligomerization and subsequent hydroisomerization. The C14-C20 olefins are oligomerized to form an oligomer distribution consisting of unreacted monomers, dimers (C28-C40) and trimers and higher oligomers (. Gtoreq.C 42). The unreacted monomers are distilled off for possible reuse in the subsequent oligomerization. The remaining oligomers were then hydroisomerized to achieve the final branching structure described herein, which consistently gave a surprising correlation of cold-start simulated viscosity (CCS) versus Noack volatility.

Definition of Hydrocarbon Properties

The following properties are used to describe the novel saturated hydrocarbon mixture:

viscosity is a physical property that measures the flow of the base stock. Viscosity is a strong function of temperature. Two common viscosity measurements are dynamic viscosity and kinematic viscosity. Dynamic viscosity measures the internal resistance to flow of a fluid. Cold Cranking Simulator (CCS) viscosity of engine oil at-35 ℃ is one example of a dynamic viscosity measurement. The international standard unit for dynamic viscosity is Pa · s. The conventional unit used is centipoise (cP), which is equal to 0.001Pa · s (or 1mPa · s). The industry slowly moves to international standards bodies. Kinematic viscosity is the ratio of dynamic viscosity to density. The international standard unit for kinematic viscosity is mm²And s. Other units commonly used in the industry are centistokes (cSt) at 40℃ (KV 40) and 100℃ (KV 100) and Saybolt Universal viscosity seconds (SUS) at 100F and 210F. Conveniently, 1mm²The/s is equal to 1cSt. ASTM D5293 and D445 are separate methods for CCS and kinematic viscosity measurements.

Viscosity Index (VI) is an empirical value used to measure the change in kinematic viscosity of a base stock as a function of temperature. The higher the VI, the smaller the relative change in viscosity with temperature. High VI base stocks are desirable for most lubricant applications, especially for multigrade automotive engine oils and other automotive lubricants that experience large operating temperature variations. ASTM D2270 is a generally accepted method for determining VI.

Pour point is the lowest temperature at which movement of the test specimen is observed. It is one of the most important properties of base stocks because most lubricants are designed to operate in the liquid phase. Low pour points are often desirable, especially in cold weather lubrication. ASTM D97 is a standard manual method of measuring pour point. It is increasingly being replaced by automated methods such as ASTM D5950 and ASTM D6749. ASTM D5950 with a1 ℃ test interval was used for pour point measurements for the examples of this patent.

Volatility is a measure of the loss of oil by evaporation at elevated temperatures. It has become a very important specification due to emissions and operating life concerns, especially for light grade base stocks. The volatility depends on the molecular composition of the oil, especially at the front of the boiling point curve. Noack (ASTM D5800) is a commonly accepted method for measuring the volatility of automotive lubricants. The Noack test method itself simulates evaporative losses in high temperature use such as an operating internal combustion engine.

The boiling point profile is the boiling point range defined by the True Boiling Point (TBP) at which 5% and 95% of the material evaporates. It is measured by ASTM D2887 herein.

NMR Branch analysis

Branching parameters for hydrocarbon characterization measured by NMR spectroscopy include:

branching Index (BI): the percentage of methyl hydrogens present in the chemical shift range 0.5 to 1.05ppm among all hydrogens present in the 1H NMR chemical range 0.5 to 2.1ppm in the isoparaffins.

Branch Proximity (BP): appear in¹³Percent of repeating methylene carbons at C NMR chemical shift 29.8ppm with four or more carbon atoms removed from the end groups or branches.

Internal alkyl carbon: is the number of methyl, ethyl or propyl carbons removed from the terminal methyl carbon by three or more carbons, including 3-methyl, 4-methyl, 5+ methyl, adjacent methyl, internal ethyl, n-propyl and the like¹³Unknown methyl groups with C NMR chemical shifts between 0.5ppm and 22.0ppm, except for the terminal methyl carbon which appears at 13.8 ppm.

5+ methyl carbon: is the number of methyl carbons in the average isoparaffin molecule present at 13C NMR chemical shift 19.6ppm attached to methine carbons more than four carbons from the terminal carbon.

The NMR spectra were obtained using a Bruker AVANCE 500 spectrometer using a 5mm BBI probe. Each sample was mixed with CDCl at a ratio of 1₃And (4) mixing.¹H NMR was recorded at 500.11MHz and 9.0 μ s (30 ℃) pulses applied at 4s intervals were used, and 64 simultaneous additions were made to each spectrumAnd (6) scanning.¹³C NMR was recorded at 125.75MHz using a 7.0 μ s pulse and applied at 6 second intervals using inverse gated decoupling, and 4096 scans were added simultaneously per spectrum. Adding a small amount of 0.1M Cr (acac)₃As relaxant, and TMS as internal standard.

The branching properties of the lubricant base stock samples of the present invention were determined according to the following six-step method. The procedure is provided in detail in US20050077208A1, which is incorporated herein in its entirety. The following procedure was slightly modified to characterize the sample sets of the present invention:

1) Identifying CH branch centers and CH using DEPT pulse sequences₃Branch endpoints (Doddrell, D.T.; D.T. Pegg; M.R. Bendall, journal of Magnetic Resonance 1982, 48, 323 and beyond).

2) APT pulse sequences were used to verify the absence of carbon (quaternary carbon) triggering multiple branches (pat, s.l.; wood, journal of Magnetic Resonance 1982, 46, 535 and beyond).

3) Tabulated values and calculated values are used to assign various branched carbon resonances to specific branched positions and lengths (Lindeman, l.p., journal of Qualitative Analytical Chemistry 43, 1971 1245 and beyond; netzel, d.a. et al, fuel,60, 1981, 307 and beyond).

Branched NMR chemical shifts (ppm)

Table 2: description of ppm Shift of alkyl Branch by carbon NMR

4) The relative frequency of branches appearing at different carbon positions is quantified by comparing the integrated intensity of its terminal methyl carbons with the intensity of single carbons (total carbon integrated/number per molecule in the mixture). For example, the number of 5+ methyl branches per molecule is calculated from the signal intensity at a chemical shift of 19.6ppm relative to the intensity of a single carbon.

For the unique case of 2-methyl branching, where both the terminal and branching methyl groups occur at the same resonance position, the intensity is divided by 2 before making branch occurrence frequency calculations.

If the 4-methyl branch score is calculated and tabulated, its contribution to the 5+ methyl group must be subtracted to avoid double counting.

The unknown methyl branches were calculated from the contribution of the signal appearing between 5.0ppm and 22.5ppm, but do not include any of the branches reported in table 2.

5) The Branch Index (BI) and Branch Proximity (BP) are calculated using the calculations described in us patent No. 6090989, which is incorporated herein by reference in its entirety.

6) The branches found in steps 3 and 4 (except for the 2-methyl branch) were added to calculate the total internal alkyl branch per molecule. These branches will include 3-methyl, 4-methyl, 5+ methyl, endo-ethyl, n-propyl, adjacent methyl and unknown methyl groups.

FIMS analysis: the hydrocarbon distribution of the present invention is determined by FIMS (field ionization Mass Spectrometry). FIMS spectra were obtained on a Waters GCT-TOF mass spectrometer. The sample was introduced via a solid probe, which was heated from about 40 ℃ to 500 ℃ at a rate of 50 ℃/min. The mass spectrometer was scanned from m/z 40 to m/z 1000 at a rate of 5 seconds/decade. The obtained mass spectra are summed to produce one average spectrum which provides the carbon number distribution of paraffins and naphthenes containing at most 6 rings.

Hydrocarbon structure and properties

The structure of the hydrocarbon mixtures disclosed herein is characterized by FIMS and NMR. FIMS analysis confirmed that greater than 80% of the molecules in the hydrocarbon mixture had an even number of carbon numbers.

The unique branched structure of the hydrocarbon mixtures disclosed herein is characterized by NMR parameters such as BP, BI, internal alkyl branching, and 5+ methyl. BP/BI of hydrocarbon mixture ≥ 0.6037 (internal alkyl branch per molecule) +2.0. The hydrocarbon mixture has an average of 0.3 to 1.5 methyl groups per molecule.

Hydrocarbon mixtures can be divided into two carbon ranges based on carbon number distribution: C28-C40 carbons, and greater than or equal to C42. Typically, the carbon number of about or greater than 95% of the molecules present in each hydrocarbon mixture is within the specified range. Representative molecular structures in the C28-C40 range can be proposed based on NMR and FIMS analysis. Without wishing to be bound by any particular theory, it is believed that the structures made by oligomerizing and hydroisomerizing the olefins have methyl, ethyl, butyl branches distributed throughout the structure, and that the branching index and branching proximity contribute to the surprisingly good low temperature properties of the product. Exemplary structures in the hydrocarbon mixtures of the present invention are as follows:

the unique branched structure and narrow carbon distribution of hydrocarbon mixtures makes them suitable for use as high quality synthetic base oils, particularly for low viscosity engine oil applications. The hydrocarbon mixture exhibits:

KV100 is 3.0-10.0cSt;

pour point from-20 ℃ to-55 ℃;

correlation of Noack with CCS at-35 ℃ so that Noack is between 2750 (CCS at-35 ℃)^(-0.8)Plus or minus 2;

the correlation of Noack and CCS for the hydrocarbon mixtures is shown in figures 3 and 4. In each figure, the top line represents Noack =2750 (CCS at-35 ℃)^(-0.8)+2 and bottom plot represent Noack =2750 (CCS at-35 ℃)^(-0.8)-2. More preferably, the hydrocarbon mixture has a correlation of Noack and CCS at-35 ℃ such that Noack is between Noack =2750 (CCS at-35 ℃)^(-0.8)+0.5 and Noack =2750 (CCS at-35 ℃)^(-0.8)-2. It has been found that the hydrocarbon mixtures closer to the origin in fig. 3 and 4 are more favorable for low viscosity engine oils due to low volatility and reduced viscosity at-35 ℃.

In addition to the above-described properties of BP/BI, internal alkyl branching per molecule, 5+ methyl branching per molecule, and Noack/CCS correlation, a hydrocarbon mixture having a carbon number in the range of C28 to C40, and in another embodiment in the range of C28 to C36, or in another embodiment a molecule having a carbon number of C32, in accordance with the present invention will typically exhibit the following properties:

KV100 is 3.0-6.0cSt;

VI is 11ln (BP/BI) +135 to 11ln (BP/BI) +145; and

pour points were 33ln (BP/BI) -45 to 33ln (BP/BI) -35.

In one embodiment, the KV100 of the C28-C40 hydrocarbon mixture is from 3.2 to 5.5cSt; in another embodiment KV100 is 4.0 to 5.2cSt; and in another embodiment from 4.1 to 4.5cSt.

The VI of the C28-C40 hydrocarbon mixture is in one embodiment 125-155 and in another embodiment 135-145.

The pour point of the hydrocarbon mixture is in one embodiment from 25 ℃ to-55 ℃ and in another embodiment from 35 ℃ to-45 ℃.

The boiling point range of the C28-C40 hydrocarbon mixture is in one embodiment no greater than 125 ℃ (TBP at 95% to TBP at 5%), as measured by ASTM D2887; in another embodiment no greater than 100 ℃; in one embodiment no greater than 75 ℃; in another embodiment no greater than 50 ℃; and in one embodiment no greater than 30 deg.c. In preferred embodiments, those having a boiling point range of no greater than 50 ℃ and even more preferably no greater than 30 ℃ for a given KV100 produce surprisingly low Noack volatility (ASTM D5800).

The C28-C40 hydrocarbon mixture in one embodiment has a Branching Proximity (BP) of from 14 to 30 and a Branching Index (BI) of from 15 to 25; and in another embodiment BP is from 15 to 28 and BI is from 16 to 24.

The Noack volatility (ASTM D5800) of the C28-C40 hydrocarbon mixture is in one embodiment less than 16wt%; in one embodiment less than 12wt%; in one embodiment less than 10wt%; in one embodiment less than 8wt% and in one embodiment less than 7wt%. The C28-C40 hydrocarbon mixture also has in one embodiment less than 2700cP; less than 2000cP in another embodiment; less than 1700cP in one embodiment; and a CCS at-35 ℃ of less than 1500cP in one embodiment.

In addition to the above-described association of BP/BI, internal alkyl branches per molecule, 5+ methyl branches per molecule, and Noack with CCS at-35 ℃, hydrocarbon mixtures in the carbon number range of C42 and greater will generally exhibit the following characteristics:

KV100 is 6.0-10.0cSt;

VI is 11ln (BP/BI) +145 to 11ln (BP/BI) +160; and

pour points were 33ln (BP/BI) -40 to 33ln (BP/BI) -25.

The hydrocarbon mixture containing C42 carbons or greater has a KV100 of 8.0 to 10.0cSt in one embodiment, and 8.5 to 9.5cSt in another embodiment.

The VI of the hydrocarbon mixture having 42 carbons or more is in one embodiment 140 to 170; and in another embodiment from 150 to 160.

Pour point is in one embodiment-15 ℃ to-50 ℃; and in another embodiment from-20 ℃ to-40 ℃.

In one embodiment, the BP of a hydrocarbon mixture containing 42 carbons or more is from 18 to 28 and the BI is from 17 to 23. In another embodiment, the BP of the hydrocarbon mixture is from 18 to 28 and the BI is from 17 to 23.

Generally, the two hydrocarbon mixtures disclosed above exhibit the following characteristics:

according to FIMS, at least 80% of the molecules have an even number of carbon numbers;

KV100 is 3.0-10.0cSt;

pour point from-20 ℃ to-55 ℃;

correlation of Noack with CCS at-35 ℃ so that Noack is between 2750 (CCS at-35 ℃)^(-0.8)Plus or minus 2;

BP/BI per molecule of not less than-0.6037 (internal alkyl branch) +2.0; and (c) and (d),

an average of 0.3 to 1.5 5+ methyl branches per molecule.

Synthesis of

Provided herein are possible processes or methods for making the disclosed hydrocarbon mixtures. The novel hydrocarbon mixtures disclosed herein can be synthesized via olefin oligomerization to achieve the desired carbon chain lengths, followed by hydroisomerization to improve their cold flow properties such as pour point and CCS, among others. In one embodiment, the C14 to C20 length olefins are oligomerized using an acid catalyst to form an oligomer mixture. The olefins may be derived from naturally occurring molecules such as crude oil or gas-based olefins, or from ethylene polymerization. In some variations, about 100% of the carbon atoms in the olefin feedstock described herein may be derived from a renewable carbon source. For example, alpha-olefin comonomers may be produced by oligomerization of ethylene resulting from dehydration of ethanol produced from renewable carbon sources. In some variations, the alpha-olefin comonomer may be produced by dehydration of a non-ethanol primary alcohol produced from a renewable carbon source. The renewable alcohols can be dehydrated to olefins using gamma alumina or sulfuric acid. In some embodiments, the modified or partially hydrogenated terpene feedstock from a renewable resource is combined with one or more olefins from a renewable resource.

In one embodiment, the C14-C20 olefin monomer is at BF₃And/or BF promoted with a mixture of alcohol and/or ester (e.g. linear alcohol and alkyl acetate)₃In the presence of an oligomerization reaction, a Continuous Stirred Tank Reactor (CSTR) was used with an average residence time of 60 to 400 minutes. In another embodiment, the C14-C20 olefin monomer is at BF₃And/or facilitated BF₃In the presence of a continuous stirred tank reactor, an oligomerization was carried out with an average residence time of 90 to 300 minutes. In yet another embodiment, the C14-C20 olefin monomer is at BF₃And/or facilitated BF₃In the presence of a continuous stirred tank reactor, an oligomerization was carried out with an average residence time of 120 to 240 minutes. The temperature of the oligomerization reaction may be from 10 ℃ to 90 ℃. However, in a preferred embodiment, the temperature is maintained between 15 ℃ and 75 ℃ and most preferably between 20 ℃ and 40 ℃ for the duration of the reaction.

Suitable Lewis acid catalysts for the oligomerization process include metalloid halides and metal halides, such as AlCl, typically used as Friedel-crafts catalysts₃、BF₃、BF₃Complex, BCl₃、AlBr₃、TiCl₃、TiCl₄、SnCl₄And SbCl₅. Any metalloid halide or metal halide catalyst may be used, with or without a co-catalyst proton promoter (e.g., water, alcohol, acid or ester). In one embodimentThe oligomerization catalyst is selected from the group consisting of zeolites, friedri-krafft catalysts, bronsted acids, lewis acids, acidic resins, acidic solid oxides, acidic silica aluminophosphates, group IVB metal oxides, group VB metal oxides, group VIB metal oxides, hydroxides or group VIII metals in free metal form, and any combination thereof.

If the dimer moiety is saturated, it is not isomerized to a Br index of less than 100mg Br₂100g (ASTM D2710), it is necessary to properly control the oligomerization reaction temperature and residence time within the CSTR to ensure that the Branching Proximity (BP) of the dimer portion (C28-C40) of the oligomerization product is 25 to 35, preferably 27 to 35, more preferably 27 to 33, and most preferably 28 to 32. Too low a branching proximity prior to hydroisomerization will result in an isomerized hydrocarbon mixture falling below the solid line of fig. 1, and will produce a less desirable higher CCS viscosity at-35 ℃ for a given Noack volatility to meet the range shown in fig. 3 and 4. Conversely, too high a branching proximity would require greater isomerization to achieve an acceptable pour point, which would increase both Noack volatility and CCS at-35 ℃. In one embodiment, the unsaturated oligomer product is distilled to remove unreacted monomer. For example, unreacted monomer can be separated from the oligomer product, e.g., via distillation, and can be recycled back to the mixture of first and/or second starting materials used for its oligomerization.

The oligomer product is then hydroisomerized to provide the additional internal alkyl branching required to achieve the desired branching characteristics. In one embodiment, the entire oligomer product, including both dimers (C28-C40) and heavier oligomers (. Gtoreq.C42), is hydroisomerized prior to separation by distillation. The hydroisomerized product is then separated by distillation into the final hydrocarbon product. In another embodiment, the dimer and heavier oligomers are fractionated and hydroisomerized, respectively.

Hydroisomerization catalysts useful in the present invention typically comprise a shape selective molecular sieve, a metal or mixture of metals that is catalytically active for hydrogenation, and a refractory oxide support. The presence of the hydrogenation component leads to product improvements, especially VI and stability. Typical catalytically active hydrogenation metals include chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum and palladium. Platinum and palladium are particularly preferred, and platinum is most preferred. If platinum and/or palladium are used, the metal content is typically from 0.1 to 5wt%, usually from 0.1 to 2wt% and not more than 10wt% of the total catalyst. Hydroisomerization catalysts are discussed, for example, in U.S. patent nos. 7390763 and 9616419 and U.S. patent application publications 2011/0192766 and 2017/0183583.

The conditions of the hydroisomerization are tailored to achieve an isomerized hydrocarbon mixture having the specific branching properties described above, and will therefore depend on the characteristics of the feed used. The reaction temperature is generally from about 200 ℃ to 400 ℃, preferably from 260 ℃ to 370 ℃, most preferably from 288 ℃ to 345 ℃, and the Liquid Hourly Space Velocity (LHSV) is generally about 0.5h^-1To about 20h^-1. The pressure is typically from about 15psig to about 2500psig, preferably from about 50psig to about 2000psig, more preferably from about 100psig to about 1500psig. The low pressure provides enhanced isomerization selectivity, which results in greater isomerization and less cracking of the feed, thus resulting in increased yields.

Hydrogen is present in the reaction zone during the hydroisomerization process, typically in a hydrogen to feed ratio of about 0.1 to 10MSCF/bbl (thousand standard cubic feet per cylinder), preferably about 0.3 to about 5MSCF/bbl. Hydrogen may be separated from the product and recycled to the reaction zone.

In one embodiment, an additional hydrogenation step is added prior to hydroisomerization to protect the downstream hydroisomerization catalyst. In another embodiment, an additional hydrogenation or hydrofinishing step is added after the hydroisomerization to further improve the saturation and stability of the hydrocarbon mixture.

The hydroisomerized hydrocarbon mixture comprises a mixture of dimers ranging in carbon number from C28 to C40, and trimers + having carbon numbers of C42 and greater. Each hydrocarbon mixture will exhibit a BP/BI of ≧ 0.6037 (internal alkyl branching) ± 2.0 per molecule, and an average of 0.3 to 1.5 methyl branches per molecule at the fifth or greater position. Importantly, at least 80% of the molecules of each composition also have an even number of carbon numbers, as determined by FIMS. In another embodimentEach hydrocarbon composition will also exhibit a correlation of Noack to CCS at-35 ℃ such that Noack is 2750 (CCS at-35 ℃)^(-0.8)And +/-2. These characteristics allow the formulation of low viscosity engine oils as well as many other high performance lubricant products.

In one embodiment, C16 olefins are used as the feed to the oligomerization reaction. When C16 olefins are used as feed, the hydroisomerized dimer product typically exhibits a KV100 of 4.3cSt, with a Noack loss of <8%, and a CCS at-35 ℃ of about 1700cP. The very low Noack volatility is attributed to the high initial boiling point and narrow boiling point distribution when compared to other 3.9-4.4cSt synthetic base stocks. This makes it ideal for use in low viscosity engine oils with stringent volatility requirements. The excellent CCS and pour point characteristics are attributed to the branching characteristics discussed above. In one embodiment, the pour point of the material is ≦ 40 ℃. This is required to pass key engine oil formulation requirements for 0W formulations, including mini rotational viscosity (ASTM D4684) and scanning Brookfield (ASTM D2983) specifications.

Lubricant formulations

The hydrocarbon mixtures disclosed herein may be used as lubricant base stocks to formulate final lubricant products containing additives. In certain variations, a base stock prepared according to the methods described herein is blended with one or more additional base stocks such as one or more commercially available PAOs, gas-to-liquid (GTL) base stocks, one or more mineral base stocks, vegetable oil base stocks, algae-derived base stocks, a second base stock described herein, or any other type of renewable base stock. Any effective amount of additional base stock may be added to achieve a blended base oil with the desired properties. For example, the blended base oil can comprise a ratio of a first base stock described herein to a second base stock (e.g., commercially available base oil PAO, GTL base stock, one or more mineral base stocks, vegetable oil base stock, algae derived base stock, second base stock described herein) that is about 1-99%, about 1-80%, about 1-70%, about 1-60%, about 1-50%, about 1-40%, about 1-30%, about 1-20%, or about 1-10%, based on the total weight of the composition that can be manufactured.

Also disclosed herein are lubricant compositions comprising the hydrocarbon mixtures described herein. In some variations, the lubricant composition comprises a base oil comprising at least a portion of the hydrocarbon mixture produced by any of the methods described herein and one or more additives selected from the group consisting of: antioxidants, viscosity modifiers, pour point depressants, suds suppressors, detergents, dispersants, dyes, markers, rust or other corrosion inhibitors, emulsifiers, demulsifiers, flame retardants, antiwear agents, friction modifiers, thermal stability modifiers, multifunctional additives (e.g., additives that act as both antioxidants and dispersants), or any combination thereof. The lubricant composition can comprise the hydrocarbon mixture described herein and any lubricant additive, combination of lubricant additives, or available additive package.

Any of the compositions described herein used as base stocks may be present at greater than about 1%, based on the total weight of the final lubricant composition. In certain embodiments, the amount of base stock in the formulation is greater than about 2wt%, 5wt%, 15wt%, or 20wt%, based on the total weight of the formulation. In some embodiments, the amount of base oil in the composition is about 1 to 99%, about 1 to 80%, about 1 to 70%, about 1 to 60%, about 1 to 50%, about 1 to 40%, about 1 to 30%, about 1 to 20%, or about 1 to 10%, based on the total weight of the composition. In certain embodiments, the amount of base stock in a formulation provided herein is about 1%, 5%, 7%, 10%, 13%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 99% based on the total weight of the formulation.

As is known in the art, the type and amount of lubricant additives combined with the base oil are selected such that the final lubricant composition meets certain industry standards or specifications for a particular application. Generally, when used, the concentration of each additive in the composition can be about 0.001wt% to about 20wt%, about 0.01wt% to about 10wt%, about 0.1wt% to about 5wt%, or about 0.1wt% to about 2.5wt%, based on the total weight of the composition. Further, the total amount of additives in the composition can be about 0.001wt% to about 50wt%, about 0.01wt% to about 40wt%, about 0.01wt% to about 30wt%, about 0.01wt% to about 20wt%, about 0.1wt% to about 10wt%, or about 0.1wt% to about 5wt%, based on the total weight of the composition.

In some variations, the base oils described herein are formulated in lubricant compositions for use as two-cycle engine oils, transmission oils, hydraulic fluids, compressor oils, turbine oils and lubricating esters, automotive engine oils, gear oils, marine lubricants, and process oils. Process oil applications include, but are not limited to: roll-milling oils, spooling oils, plasticizers, spindle oils, polymer processing, mold release agents, coatings, adhesives, sealants, polishes and wax blends, drawing oils, and stamping oils, rubber compounding, pharmaceutical processing aids, personal care products, and inks.

In yet other variations, the base oils described herein are formulated as an industrial oil or lubricating ester formulation comprising at least one additive selected from the group consisting of: antioxidants, anti-wear agents, extreme pressure agents, antifoam agents, detergents/dispersants, rust and corrosion inhibitors, thickeners, tackifiers and demulsifiers. It is also contemplated that the base stock of the present invention may be formulated as a dielectric heat transfer fluid comprised of a blend of relatively pure compounds selected from the group consisting of aromatic hydrocarbons, polyalphaolefins, polyol esters, and natural vegetable oils, and additives for improving pour point, increasing stability, and reducing oxidation rate.

The invention will be further elucidated by the following examples, which are not intended to be limiting.

Examples

Examples 1 to 6 (C28-C40 Hydrocarbon mixture)

Example 1

1-hexadecenes with less than 8% branching and internal olefins at BF₃Oligomerization with a co-catalyst combination of butanol and butyl acetate. The reaction was maintained at 20 ℃ during the semi-continuous addition of olefin and cocatalyst. The residence time was 90 minutes. Unreacted monomer was then distilled off, leaving less than 0.1% monomer distillation bottoms. Subsequent distillation is carried out to react the dimer withTrimer + separates and less than 5% of the trimer remains in the dimer fraction.

The dimer is then hydroisomerized with an alumina-bound noble metal-impregnated MRE structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 307 ℃. The cracked molecules were separated from the hydroisomerized C16 dimers using an in-line stripper.

Example 2

The oligomerization and subsequent distillation were carried out as in example 1. The dimer is then hydroisomerized with an alumina-bound noble metal-impregnated MRE structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 313 ℃. The cracked molecules were separated from the hydroisomerized C16 dimers using an in-line stripper.

Example 3

The oligomerization and subsequent distillation were carried out as in example 1. The dimer is then hydroisomerized with an alumina-bound noble metal-impregnated MRE structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 324 ℃. The cracked molecules were separated from the hydroisomerized C16 dimers using an in-line stripper.

Example 4

The oligomerization and subsequent distillation were carried out as in example 1. The dimer is then hydroisomerized with a noble metal-impregnated MTT structure type aluminosilicate catalyst bound to alumina. The reaction was carried out in a fixed bed reactor at 500psig and 316 ℃. The cracked molecules were separated from the hydroisomerized C16 dimers using an in-line stripper.

Example 5

The oligomerization and subsequent distillation were carried out as in example 1. The dimer is then hydroisomerized with an alumina-bound noble metal-impregnated MTT structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 321 ℃. The cracked molecules were separated from the hydroisomerized C16 dimers using an in-line stripper.

Example 6

The oligomerization and subsequent distillation were carried out as in example 1. The dimer is then hydroisomerized with an alumina-bound noble metal-impregnated MTT structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 332 ℃. The cracked molecules were separated from the hydroisomerized C16 dimers using an in-line stripper.

Examples 7 to 12 (C.gtoreq.42 hydrocarbon mixture)

Example 7

1-hexadecenes with less than 8% branching and internal olefins at BF₃Oligomerization with a co-catalyst combination of butanol and butyl acetate. The reaction was maintained at 20 ℃ during the semi-continuous addition of olefin and cocatalyst. The residence time was 90 minutes. Unreacted monomer was then distilled off, leaving less than 0.1% monomer distillation bottoms. Subsequent distillation was performed to separate the dimer from the trimer and higher oligomers, with the dimer formed having less than 5% trimer.

The trimer and higher oligomer (trimer +) fractions are then hydroisomerized with a noble metal-impregnated MRE structure type aluminosilicate catalyst incorporating alumina. The reaction was carried out in a fixed bed reactor at 500psig and 313 ℃. The cracked molecules were separated from the hydroisomerized C16 trimer + using an in-line stripper.

Example 8

The oligomerization and subsequent distillation were carried out in the same manner as in example 7. The trimer + fraction is then hydroisomerized with a noble metal-impregnated MRE structure type aluminosilicate catalyst incorporating alumina. The reaction was carried out in a fixed bed reactor at 500psig and 318 ℃. The cracked molecules were separated from the hydroisomerized C16 trimer + using an in-line stripper.

Example 9

The oligomerization and subsequent distillation were carried out in the same manner as in example 7. The trimer + fraction is then hydroisomerized with an alumina-bound noble metal-impregnated MRE structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 324 ℃. The cracked molecules were separated from the hydroisomerized C16 trimer + using an in-line stripper.

Example 10

The oligomerization and subsequent distillation were carried out in the same manner as in example 7. The trimer + fraction is then hydroisomerized using an alumina-bound noble metal-impregnated MTT structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 321 ℃. The cracked molecules were separated from the hydroisomerized C16 trimer + using an in-line stripper.

Example 11

The oligomerization and subsequent distillation were carried out in the same manner as in example 7. The trimer + fraction is then hydroisomerized using an alumina-bound noble metal-impregnated MTT structure type aluminosilicate catalyst. The reaction was carried out in a fixed bed reactor at 500psig and 327 ℃. The cracked molecules were separated from the hydroisomerized C16 trimer + using an in-line stripper.

Example 12

The oligomerization and subsequent distillation were carried out in the same manner as in example 7. The trimer + fraction is then hydroisomerized with a noble metal-impregnated MTT structure type aluminosilicate catalyst incorporating alumina. The reaction was carried out in a fixed bed reactor at 500psig and 332 ℃. The cracked molecules were separated from the hydroisomerized C16 trimer + using an in-line stripper.

The results of the examination of the hydrocarbon mixtures obtained in examples 1 to 12 are summarized in table 3 below.

TABLE 3

* NM: not measured

Comparative GTL and PAO base stocks

The results of characterization of comparable GTL and PAO samples used in figures 1-4 are summarized in table 4. GTL comparative examples are shown in the following publications: GTL #1WO2007068795, GTL #2WO2007068795, GTL #3US2005007720.PAO comparative examples PAO was measured on commercially available samples using the techniques described above.

TABLE 4

When the foregoing data are graphically depicted, the important structural and performance differences of the hydrocarbon mixtures of the present invention as compared to prior art hydrocarbon mixtures are clearly seen and support the surprisingly improved performance of the hydrocarbon mixtures of the present invention. Fig. 1-4 graphically depict a number of the above-described features.

FIG. 1 shows the correlation between BP/BI and internal alkyl branches per molecule for various hydrocarbon mixtures. The straight line in the figure depicts BP/BI = -0.6037 (internal alkyl branches per molecule) +2.0. The total hydrocarbon mixture of the invention is above the line. Although several prior art hydrocarbon mixtures are also above the line, they do not meet the other important characteristics of the hydrocarbon mixtures of the present invention, as shown in fig. 2-4.

FIG. 2 shows the correlation between BP/BI and 5+ methyl branches per molecule for various hydrocarbon mixtures. It demonstrates that the 5+ methyl branch per molecule of the hydrocarbon mixture of the present invention falls within a unique range of 0.3 to 1.5. All prior art mixtures fall outside the stated range.

FIGS. 3 and 4 show the correlation between NOACK volatility and CCS at-35 ℃ for various hydrocarbon mixtures. Additionally included are some commercially available group III base oils that do not meet the requirement of an even number of carbon numbers of 80% by FIMS. The solid and dashed lines depict the upper and lower limits of Noack compared to CCS at-35 ℃, respectively, exhibited by the unique hydrocarbon mixtures of the present invention, which are Noack =2750 (CCS at-35 ℃)^(-0.8)+2 and NOACK =2750 (CCS at-35 ℃)^(-0.8)-2. It can be seen that all of the hydrocarbon mixtures of the present invention fall within the stated ranges, while substantially all of the prior art samples fall outside the stated ranges, exceptIn addition to the higher viscosity PAO, the PAO has no desired branching (as seen in fig. 1 and 2). FIG. 4 is an enlarged view of the CCS range of 800-2800cP at-35 deg.C of FIG. 3. Generally, for engine oil formulations, the preferred base stock will fall as close as possible to the origin of FIGS. 3 and 4, since for a given CCS viscosity at-35 ℃, a lower Noack volatility is desirable for modern engine oil formulations such as 0W-20 to 0W-8 formulations.

The foregoing data and figures demonstrate the unique branching characteristics (characterized by NMR) and the unique properties resulting from the hydrocarbon mixtures of the present invention. It has been found that the combination of new structural properties results in outstanding properties, including very low volatility and good low temperature properties, which are important performance attributes of high quality base stocks.

Claims (19)

1.A hydrocarbon mixture wherein:

a. according to FIMS, the percentage of molecules with even number of carbon numbers is more than or equal to 80%;

BP/BI ≥ 0.6037 × (internal alkyl branch per molecule) +2.0;

c. an average of 0.3 to 1.5 5 methyl groups per molecule; and

d. has a correlation between Noack volatility and cold start simulated CCS viscosity at-35 ℃, wherein the Noack volatility is 2750 × (CCS viscosity at-35 ℃), and^(-0.8)the content of the carbon dioxide is within +/-2,

wherein BP represents the branch proximity, which is present in¹³The percentage of repeating methylene carbons at C NMR chemical shift 29.8ppm with four or more carbon atoms removed from the end groups or branches,

BI denotes the branching index, which is present in the isoparaffin, in the isoparaffin¹The percentage of methyl hydrogens present in the chemical shift range of 0.5 to 1.05ppm among all hydrogens in the chemical range of 0.5 to 2.1ppm of H NMR,

internal alkyl branching is meant to include, in addition to the terminal methyl carbon appearing at 13.8ppm, 3-methyl, 4-methyl, 5+ methyl, adjacent methyl, internal ethyl, n-propyl and the like appearing at¹³C NMR chemical shifts of between 0.5ppm and 22.0ppm of unknown methyl groups,the number of methyl, ethyl or propyl carbons from which three or more carbons are removed from the terminal methyl carbon,

5+ methyl means that the average isoparaffin molecule appears in¹³The number of methyl carbons attached to a methine carbon more than four carbons from the end carbon at a C NMR chemical shift of 19.6ppm,

the CCS viscosity is determined according to ASTM D5293 and the Noack volatility is determined according to ASTM D5800.

2. The mixture of claim 1, wherein the mixture further has a correlation of Noack volatility to cold start simulated CCS viscosity at-35 ℃, wherein Noack volatility is between 2750 x (CCS viscosity at-35 ℃)^(-0.8)+0.5 and 2740 × (CCS viscosity at-35 ℃), and^(-0.8)-2.

3. The hydrocarbon mixture of claim 1, further comprising the following properties:

KV100 is 3.0-10.0cSt; and

f. the pour point is between-20 ℃ and-55 ℃,

where KV100 denotes the kinematic viscosity at 100 deg.C, as determined by ASTM D445.

4. The hydrocarbon mixture of claim 3, wherein the carbon number of the hydrocarbon mixture is 28-40 and the hydrocarbon mixture further exhibits the following characteristics:

KV100 is 3.0-6.0cSt;

VI is 11ln (BP/BI) +135 to 11ln (BP/BI) +145; and

c. pour points were 33ln (BP/BI) -45 to 33ln (BP/BI) -35,

where VI denotes the viscosity index, which is an empirical value used to measure the change in kinematic viscosity of the base stock as a function of temperature, and VI is determined according to ASTM D2270.

5. The hydrocarbon mixture of claim 4, wherein the boiling point range of the hydrocarbon mixture is no greater than 125 ℃, i.e., 95% TBP to 5% TBP, wherein the TBP represents the true boiling point as measured by ASTM D2887.

6. The hydrocarbon mixture of claim 4, wherein the boiling point range of the hydrocarbon mixture is no greater than 50 ℃, i.e., 95% TBP to 5% TBP, wherein the TBP represents the true boiling point as measured by ASTM D2887.

7. The hydrocarbon mixture of claim 4, wherein its branching proximity is from 14 to 30 and branching index is from 15 to 25.

8. A hydrocarbon mixture according to claim 4, wherein its KV100 is between 3.2 and 5.5cSt.

9. The hydrocarbon mixture of claim 4, wherein its VI is from 135 to 145.

10. The hydrocarbon mixture of claim 4, wherein its pour point is-25 ℃ to-55 ℃.

11. A hydrocarbon mixture as claimed in claim 4, wherein its Noack volatility is less than 16wt%.

12. A hydrocarbon mixture according to claim 3, wherein it has a CCS viscosity at-35 ℃ of less than 2000cP.

13. The mixture according to claim 3, wherein the hydrocarbon mixture has a carbon number ≧ 42 and has the following characteristics:

KV100 is 6.0-10.0cSt;

VI is 11ln (BP/BI) +145 to 11ln (BP/BI) +160; and

c. pour points were 33ln (BP/BI) -40 to 33ln (BP/BI) -25.

14. The hydrocarbon mixture of claim 13 wherein its BP is 16 to 30 and BI is 15 to 25.

15. A hydrocarbon mixture according to claim 13, wherein its KV100 is from 8.0 to 10.0cSt.

16. The hydrocarbon mixture of claim 13, wherein its VI is 140-170, and VI represents a viscosity index, which is an empirical value for measuring the change in kinematic viscosity of a base stock as a function of temperature, and VI is determined according to ASTM D2270.

17. The hydrocarbon mixture of claim 13, wherein its pour point is-15 ℃ to-50 ℃.

18. A lubricant composition comprising from 1 to 99wt% of the hydrocarbon mixture of claim 1 as a base stock component, and one or more additives selected from the group consisting of: antioxidants, viscosity modifiers, pour point depressants, suds suppressors, detergents, dispersants, dyes, markers, rust or other corrosion inhibitors, emulsifiers, demulsifiers, flame retardants, anti-wear agents, friction modifiers, thermal stability modifiers or multifunctional additives.

19. The lubricant composition of claim 18 formulated for use in a two-stroke engine; as a transmission fluid; as a hydraulic fluid; for a compressor; for a turbine; for automotive engine oils; as a marine grade lubricant; as a lubricating ester; as an industrial oil; as a dielectric heat transfer fluid; or as process oil.

Images